1-Halomethyl-2-alkoxyethyl acrylates and methacrylates

ABSTRACT

1-Halomethyl-2-alkoxyethyl acrylates and methacrylates useful for making acrylate and methacrylate polymers and copolymers. Preferred monomers are used to prepare fluorochemical copolymers which impart oil and water repellency to cellulosic materials and textile fibers. The fluorochemical copolymers are derived (by weight) from about 1 to 30% of the preferred monomers, 60 to 80% fluorochemical acrylate, 1 to 15% glycidyl acrylate or methacrylate, 1 to 6% of certain cationic acrylates or methacrylates, and 0 to 20% vinylidene chloride.

TECHNICAL FIELD

This invention relates to monomers for use in making acrylate andmethacrylate polymers and copolymers. This invention also relates tomonomers for use in making fluorochemical copolymers which impart oiland water repellency to various substrates.

BACKGROUND ART

Various fluorochemical wet pick-up and internal sizing agents for papertreatment are described, for example, in Rengel and Young, "InternalSizing of Paper and Paperboard", Tappi monograph series number 33, pp.170-189 (1971), Colbert, "Fluorochemicals-Fluid Repellency for Non-wovenSubstrates", Tappi, The Journal of the Technical Association of the Pulpand Paper Industry, 59, 9, (September, 1976), Banks, Ed., OrganofluorineChemicals and their Industrial Applications, pp. 231-234 (1979), andSchwartz, "Oil Resistance Utilizing Fluorochemicals", Tappi conferencepreprint, 1980 Sizing Short Course, Atlanta, Ga. Several fluorochemicalphosphates have been approved by the United States Food and DrugAdministration for use on paperboard in direct contact with food forhuman consumption. These fluorochemical phosphates can be used as wetpick-up or as internal treatments. They primarily provide oilresistance, and are used on paper plates, bags for bakery goods, cartonsand trays for oil fried foods (e.g., French fries), and in bags andcartons for pet foods.

The advent in recent years of the microwave oven has created a need fornon-metallic containers for cooking or food-warming which haveresistance to both oily and aqueous foods at oven temperatures, sincemetallic containers (e.g., aluminum trays) do not efficiently cook foodsin microwave ovens and may promote electrical arcing if the metalliccontainer walls approach or touch the walls of the microwave oven. Asuitable non-metallic food container should also withstand freezingtemperatures and conventional oven temperatures because foods sold insuch containers will often be frozen and will be cooked in bothmicrowave and conventional ovens. Cooking times for foods stored in suchcontainers usually range from a few minutes to sixty minutes or more,and cooking temperatures usually range from about 95° C. to 240° C. orhigher.

Existing commercially available fluorochemical phosphate sizingtreatments do not provide sufficient high temperature water repellencyto ovenable paperboard food trays exposed to cooking conditions forextended periods of time. Food packages have had to employ othercontainer materials or constructions to obtain adequate ovenability. Forexample, formed food trays can be made entirely from plastics such aspolyethylene terephthalate. Also, laminated, stamped food trays can bemade from a layer of conventional paperboard coated on the food sidewith a thin (0.25 to 0.33 millimeters) film of extruded polyester. Foodcontainers made entirely from plastic are relatively expensive, consumescarce petroleum resources, and lose rigidity at elevated temperatures.Food containers made from laminated paperboard and polyester sheets canbecome stained with oil on the unprotected outside surface (e.g., duringfood filling operations), are prone to rupture of the container atcorners during tray-forming operations (due in part to differences inmoisture content within the paperboard sheet), are susceptible todelamination when foods are heated to very high temperatures (e.g., whenbacon or sausage are heated in microwave or conventional ovens), and arerelatively expensive, requiring about 110 grams of polyester resin perkilogram of paperboard. In addition, scrap or waste paperboard from trayforming or other operations performed on paperboard/polyester laminateis not repulpable, and this scrap is sometimes as much as 25 percent ofthe total paperboard/polyester laminate consumed.

DISCLOSURE OF INVENTION

The present invention provides, in one aspect, novel monomers for use inmaking acrylate and methacrylate polymers and copolymers. The monomersof the invention are 1-halomethyl-2-alkoxyethyl acrylates ormethacrylates. A preferred class of such monomers have the formula:

    R.sup.1 O[CH.sub.2 CH(CH.sub.2 X)O].sub.n [C(O)CH.sub.2 O]mCOCR.sup.2 ═CH.sub.2                                             I

wherein R¹ is a substituted or unsubstituted C₁₋₂₀ alkyl, cycloalkyl, oraralkyl group which can contain divalent catenary oxygen or sulfuratoms, R² is H or methyl, X is a halogen atom, n is 1 to about 10, and mis zero or 1.

DETAILED DESCRIPTION

In the practice of the present invention, the monomers of Formula I canbe prepared using conventional methods. Monomers in which m is zero canbe prepared, for example, by reacting an alcohol with epichlorohydrin,and reacting the resulting adduct with acryloyl chloride, methacryloylchloride, acrylic acid, or methacrylic acid. Monomers in which m is 1can be prepared, for example, by reacting the above-described adduct ofalcohol and epichlorohydrin with chloroacetic acid, and combining theproduct of the latter reaction with acrylic acid or methacrylic acid.The above-described syntheses are generally carried out in the presenceof suitable catalysts or acid acceptors, e.g., an acid catalyst foresterification with acrylic acid or methacrylic acid or a tertiary aminefor esterification with acryloyl chloride or methacryloyl chloride. Forany of the above-described syntheses, the final product can, if desired,be purified (e.g., by distillation, acid wash, or base wash) to removeresidual acids, acid chlorides, catalysts, acid acceptors and otherimpurities or by-products.

The monomers of the present invention can be used to make acrylate ormethacrylate polymers or copolymers using techniques known to thoseskilled in the art. The resulting polymers and copolymers can be curedusing conventional techniques, (e.g., by free-radical polymerization, orby using ultraviolet radiation or electron beam curing) to form, forexample, decorative or protective coatings or films, potting compounds,molding resins, adhesives, or sealants. The monomers of the presentinvention are less hydrophilic than correspondingnon-halomethyl-containing monomers, and thus have particular utility forthe making of polymers or copolymers in which reduced hydrophilicity isdesired. The halomethyl group in the monomers of this invention canimpart flame retardant properties and/or a site for attack bynucleophilic agents (e.g., crosslinking agents or reactive substrates),and the monomers of this invention are therefore useful for makingpolymers or copolymers where flame retardancy or susceptibility toreaction with nucleophilic agents is desired.

A preferred use for the monomers of this invention involves the makingof fluorochemical copolymers, e.g. copolymers of the monomers of thisinvention with fluorinated monomers such as fluorochemical acrylates ormethacrylates. A preferred subclass of the monomers of Formula I havebeen found which provide useful fluorochemical copolymers described ingreater detail below. These fluorochemical copolymers impart hightemperature oil and water repellency to cellulosic materials, or oil andwater repellency to textile fibers, and comprise (by weight) about:

(a) 1 to 30% of polymer chain repeat units derived from halogenatedalkyl or alkoxyalkyl acrylate monomer(s) of formula I, above, wherein R¹is a C₁₋₂₀ alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R² isH, and m is zero or 1;

(b) 60 to 80% of polymer chain repeat units derived from fluoroacrylatemonomer(s) of the formula:

    (R.sub.f).sub.p QOCOCH═CH.sub.2                        II

wherein R_(f) is a fluoroaliphatic radical-containing group having 3 to20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1or 2;

(c) 1 to 15% of polymer chain repeat units derived from monomer(s) ofthe formula: ##STR1## wherein R³ is H or methyl; (d) 1 to 6% of polymerchain repeat units derived from cationic monomer(s) of the formula:

    CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.-                   IV

wherein R⁴ is H or methyl, Z is a divalent electron-withdrawing groupwhich activates free-radical polymerization, Y⁺ is a monovalentcationogenic group, and X⁻ is a water solubilizing anion; and

(e) 0 to 20% of polymer chain repeat units derived from vinylidenechloride;

with the proviso that the weight percent of carbon-bonded fluorine insaid copolymers is at least about 15%.

In the monomer of Formula I, R¹ is straight chain, branched, or cyclic,e.g., CH₃ (CH₂)₈ CH₂ --, CH₃ (CH₂)₃ --, CH₃ CH₂ --, CH₃ 13, (CH₃)₂ CHCH₂H₄ --, (CH₃)₃ C--, (CH₃)₂ CH--, CH₃ (CH₂)₄ CH(C₂ H₅)CH₂ --, C₆ H₁₁ --,Cl(CH₂)₄ --, Cl(CH₂)₃ --, Cl(CH₂)₂ --, ClCH₂ CH(CH₂ Cl)--, CH₃ CH(CH₂Cl)--, CH₃ CHClCH₂ --, CH₃ CH₂ O(C₂ H₄ O)₅ C₂ H₄ --, C₄ H₉ SC₃ H₆ --, orC₆ H₅ CH₂ --. R¹ preferably is a C₁₋₂₀ alkyl, cycloalkyl, haloalkyl, orhalocycloakyl radical, more preferably is a C₁₋₅ alkyl radical, and mostpreferably is CH₃ -- or CH₃ CH₂ --. R² preferably is H. Preferably X ischlorine. Preferably n is 1 to about 3, and most preferably n is 1.Preferably m is zero. Preferably, about 10 to 10 weight percent of themonomers of Formula I are used to form the above-describedfluorochemical copolymers.

Representative monomers of Formula I include the acrylate monomers CH₃OCH₂ CH(CH₂ Cl)OCOCH═CH₂, CH₃ OCH₂ CH(CH₂ Cl)OC(O)CH₂ OCOCH═CH₂, CH₃O[CH₂ CH(CH₂ Cl)O]₃ COCH═CH₂, CH₃ CH₂ OCH₂ CH(CH₂ Cl)OCOCH═CH₂, CH₃(CH₂)₂ OCH₂ CH(CH₂ Cl)OCOCH═CH₂, CH₃ CH₂ OCH₂ CH(CH₂ Br)OCOCH═CH₂,(CH₃)₂ CHOCH₂ CH(CH₂ Cl)OCOCH═CH₂, CH₃ (CH₂)₃ COCH₂ CH(CH₂ Cl)OCOCH═CH₂,(CH₃)₃ COCH₂ CH(CH₂ Cl)OCOCH═CH₂, (CH₃)₂ CH(CH₂)₂ OCH₂ CH(CH₂Cl)OCOCH═CH₂, Cl(CH₂)₂ OCH₂ CH(CH₂ Cl)OCOCH═CH₂, Br(CH₂)₂ OCH₂ CH(CH₂Cl)OCOCH═CH₂, CH₃ CH₂ O(C₂ H₄ O)₅ C₂ H₄ O[CH₂ CH(CH₂ Cl)O]₁₀ COCH═CH₂,C₄ H₉ SC₃ H₆ OCH₂ CH(CH₂ Cl)OCOCH═CH₂, and C₆ H₅ CH₂ OCH₂ CH(CH₂Cl)OCOCH═CH₂, as well as the methacrylates corresponding to the aboveacrylates.

The R_(f) substituent of the monomers of Formula II, above is amonovalent, fluorinated, aliphatic, preferably saturated, organicradical having at least three carbon atoms and as many as twenty carbonatoms. The skeletal chain of R_(f) can be straight, branched, or, ifsufficiently large, cyclic, and can include catenary divalent oxygenatoms or trivalent nitrogen atoms bonded only to carbon atoms.Preferably, R_(f) is fully fluorinated, but carbon-bonded hydrogen orchlorine atoms can be present as substituents on the skeletal chain ofR_(f), provided that not more than one atom of either hydrogen orchlorine is present for every two carbon atoms in the skeletal chain ofR_(f), and further provided that R_(f) contains at least a terminalperfluoromethyl group. While R_(f) radicals containing a large number ofcarbon atoms will function adequately, radicals containing not more thanabout 14 carbon atoms are preferred since larger radicals usuallyrepresent a less efficient utilization of fluorine that is possible withsmaller radicals. Preferably, R_(f) has an average of about 6 to 10carbon atoms.

Q in Formula II, above is an organic polyvalent (e.g., divalent) acrylicor alicyclic radical of 1 to about 12 carbon atoms, or a polyvalent(e.g., divalent) aromatic radical of about 3 to 12 carbon atoms. Q cancontain, for example, skeletal nitrogen, oxygen, or sulfur atoms, orcarbonylimino, sulfonylimino, imino, or carbonyl radicals. Q isunsubstituted for substituted by halogen atoms, hydroxyl, alkyl, or arylradicals, and preferably is free from aliphatic unsaturation. Suitable Qradicals include --CH₂ --, --C₂ H₄ --, --C₄ H₈ --, --C₆ H₄ --, --C₆ H₃<, --CH₂ C₆ H₄ CH₂ --, --C₂ H₄ SC₂ H₄ --, --C₂ H₄ OC₄ H₈ --, --CH₂ OC₂H₄ --, --SO₂ N(R⁵)C₂ H₄ --, --CON(R⁵ (C₂ H₄ --, --C₃ H₆ CON(R⁵)C₂ H₄ --,--C₂ H₄ N(R⁵)C₂ H₄ --, --COOCH₂ C(CH₃)₂ CH--, --SO₂ N(R⁵)CH₂ CH(CH₃)--,and --C₂ H₄ SO₂ N)R⁵)C₄ H₈ --, wherein R⁵ is H or a C₁₋ alkyl radical.Preferably, Q is --CH₂ --, --C₂ H₄ --, or --SO₂ N(R⁵)C₂ H₄ --.

Preferably, the monomers of Formula II contain at least about 30 weightpercent fluorine and more preferably about 40 to 60 weight percentfluorine. Preferably, about 65 to 75 weight percent of the monomers ofFormula II are used to form the above-mentioned fluorochemicalcopolymers.

Representative monomers of Formula II include C₈ F₁₇ SO₂ N(CH₃)CH₂ CH₂OCOCH═CH₂, C₆ F₁₃ C₂ H₄ SC₂ H₄ OCOCH═CH₂, C₂ F₅ C₆ F₁₀ CH₂ OCOCH═CH₂, C₇F₁₅ CH₂ OCOCH═CH₂, C₇ F₁₅ CON(CH₃)C₂ H₄ OCOCH═CH₂, (CF₃)₂ CF(CF₂)₆ CH₂CH(OH)CH₂ OCOCH═CH₂, (CF₃)₂ CFOC₂ F₄ C₂ H₄ OCOCH═CH₂, C₈ F₁₇ C₂ H₄ SO₂N(C₃ H₇)C₂ H₄ OCOCH═CH₂, C₇ F₁₅ C₂ H₄ CONHC₄ H₈ OCOCH═CH₂, ##STR2## C₈F₁₇ SO₂ N(C₂ H₅)C₄ H₈ OCOCH═CH₂, (C₃ F₇)₂ C₆ H₃ SO₂ N(CH₃)C₂ H₄OCOCH═CH₂, ##STR3## C₈ F₁₇ CF═CHCH₂ N(CH₃)C₂ H₄ OCOCH═CH₂.

In the monomers of Formula III, above, R³ preferably is methyl.Preferably, about 3 to 10 weight percent of the monomers of Formula IIIare used to form the above-mentioned fluorochemical copolymers.

In the monomer of Formula IV, above, the Z group has a carbonyl oraromatic group or an oxygen or sulfur atom bonded directly to thevinylidene group of the monomer. The Z group can be, for example,--COO(CH₂)_(p) --, --CO(CH₂)_(p) --, --CONH(CH₂)_(p) --, --OCO(CH₂)_(p)--, --O(CH₂)_(p) --, --S(CH₂)_(p) --, --C₆ H₄ --, or --C₆ H₄ (CH₂)_(p)--, where p is 1 to 10. The polymethylene moiety --(CH₂)_(p) -- and thearomatic moiety --C₆ H₄ -- in such structures can be substituted withsubstituent groups or atoms which do not interfere with free-radicalpolymerization, such as alkyl, aryl, or hydroxyl groups or halogenatoms. The R⁴ group preferably is CH₃ --. The Z group preferably isselected from --COOCH₂ CH(OH)CH₂ --, --COO(CH₂)_(k) --, or--CONH(CH₂)_(k) --, where k is 2 to 6. Useful Y⁺ groups include (a) thepyridinium ion ##STR4## (b) the ion N⁺ (R⁶)₃ where each R⁶ independentlyis H or a C₁₋₄ alkyl group, or where any two of R⁶ combine to form analkylene group having 4 to 5 chain carbon atoms, or any two of R⁶ are--CH₂)₂ -- and combine with an oxygen atom to form the moiety --CH₂)₂O(CH₂)₂ --, (c) phosphonium ions, and (d) sulfonium ions. Preferably, Y⁺is N³⁰ (R⁷)₃ where each R⁷ independently is a C₁₋₄ alkyl group. Theanion X⁻ is a matter of choice, and ordinarily is selected based uponthe method of synthesis of the cationic monomer. X⁻ preferably isselected fron halide ions such as Cl⁻, Br⁻, I⁻, and alkyl sulfate ionssuch as CH₃ OSO₃ ⁻. Preferably, about 2 to 4 weight percent of themonomers of Formula IV are used to form the above-describedfluorochemical copolymers.

Representative monomers of Formula IV include CH₂ ═C(CH₃)COOC₂ H₄ N⁺(CH₃)₃ Cl⁻, CH₂ ═CHCOOC₂ H₄ N⁺ (CH₃)₃ Cl⁻, CH₂ ═C(CH₃)COOC₂ H₄ N⁺ (CH₃)₃⁻ OSO₃ CH₃, CH₂ ═C(CH₃)COOCH₂ CH(OH)CH₂ N⁺ (CH₃)₃ Cl⁻, CH₂ ═C(CH₃)CONHC₃H₆ N⁺ (CH₃)₃ Cl⁻, CH₂ ═C(CH₃)COOC₂ H₄ N⁺ (C₂ H₅)₂ H Cl⁻, ##STR5## andCH₂ ═CHC₆ H₄ CH₂ N⁺ (CH₃)₃ Cl⁻.

Many of the above-described fluorochemical copolymers providecommercially useful water repellency immediately after applicationthereof to cellulosic materials. In contrast, fluorochemical copolymersmade by batch processes and derived from a non-halomethyl-containingmonomer in place of the monomer of Formula I, above, do not providecommercially useful water repellency immediately after applicationthereof to cellulosic materials. Instead, when the latter fluorochemicalcopolymers are applied to cellulosic materials, aging (by heating for afew minutes or more at elevated temperature or by equilibration for afew days or more at ambient temperature) generally is required to obtaincommercially useful water repellency.

The performance of paperboard, or of textile fibers, which have beentreated with the above-described fluorochemical copolymers is affected,in part, by the types and amounts of monomers from which suchfluorochemical copolymers are derived. For example, use of increasedamounts of the monomers of Formula I or Formula II tends to enhance oiland water repellency of the treated paperboard or textile fiber. Use ofincreased amounts of the monomer of Formula III tends to enhance waterrepellency, but can detract from oil repellency. Use of increasedamounts of the monomer of Formula IV tends to enhance efficientdeposition of the fluorochemical copolymer onto cellulosic or textilefibers. Also, this latter monomer aids in emulsifying the fluorochemicalcopolymer and in stabilizing the emulsion in which the copolymer can beprepared, thereby enabling the use of reduced levels of otheremulsifiers. Vinylidene chloride, if used, tends to enhance waterrepellency, and serves as a compatible "filler" monomer in thefluorochemical copolymer. Where higher weight percentages of the monomerof Formula I are used, then lesser amounts of vinylidene chloride arerequired, enabling the amount of vinylidene chloride to be reduced tozero if desired.

Minor, non-interfering amounts of monomers other than those describedabove can also be incorporated into the fluorochemical copolymers. Forexample, the fluorochemical copolymers can contain up to about 10 weightpercent of polymer units derived from ethylene, vinyl acetate, vinylchloride, vinyl fluoride, vinylidene fluoride, vinyl chloroacetate,acrylonitrile, vinylidene cyanide, styrene, alkyl styrenes, halogenatedstyrenes, methacrylonitrile, N-vinylcarbazole, vinylpyridine, vinylalkyl ethers, vinyl alkyl ketones, butadiene, chloroprene, fluoroprene,isoprene, and mixtures thereof.

Non-interfering amounts of, for example, alkyl or alkoxyalkylmethacrylates, fluorochemical methacrylates, fluorochemicalalkoxyalkylmethacrylates, acids such as acrylic acid, methacrylic acid,or chloroacetic acid (most particularly acrylic acid), or hydroxylcontaining vinyl monomers (particularly those containing terminalhydroxyl functionality, such as N-methylolacrylamide and 2-hydroxyethylacrylate) can be incorporated into the fluorochemical copolymers, butthe use thereof preferably is avoided, as their presence in thefluorochemical copolymers detracts from the oil and water repellency, ordelays the attainment of commercially acceptable water repellency, forpaperboard or textile fiber treated therewith.

The fluorochemical copolymers can be prepared using known techniques foremulsion or solution polymerization. In order to prepare treatedpaperboard, the fluorochemical copolymers preferably are applied asinternal (i.e., "wet-end") additives to an aqueous suspension ofcellulosic fibers, using conventional papermaking equipment andtechniques known to those skilled in the art of papermaking. Thefluorochemical copolymer is added to the furnish in amounts sufficientto provide the desired level of oil and water repellency. In general,these amounts are between about 0.2 to 2 percent fluorochemicalcopolymer based on weight of fibers. For reasons of economy, it ispreferred to employ a low level of fluorochemical copolymer, coincidentwith attainment of adequate oil and water repllency in the finishedpaperboard product. Following addition of the fluorochemical copolymer,the furnish is processed using conventional papermaking technology.

Treated paperboard can also be prepared by applying the fluorochemicalcopolymers using wet pick-up methods, such as a size press or calendarstack. If desired, sequential internal and wet pick-up application ofthe fluorochemical copolymers can be employed.

Some treated paperboard made using fluorochemical copolymers derivedfrom monomers of the present invention attains maximum water repellencyafter aging (see, e.g., the treated paperboard of copolymer Example 10,below). Little or no aging will be required for many otherfluorochemical copolymers exemplified below.

The fluorochemical copolymer-treated paperboard can be formed intocontainers (e.g., trays) using conventional techniques (e.g., the"Sprinter", "Kliclok", "Peerless", or molded pulp methods). Becauseinternally-applied fluorochemical copolymers penetrate uniformlythroughout the paper web, aggressive die stamping, folding, or creasingof the treated paperboard will not expose untreated fibers, and the oiland water repellency of the treated paperboard will not be materiallylessened by tray-forming operations. Also, if a moisturizing step isused during container-forming, the treated paperboard will have a moreuniform moisture content than moisturized paperboard/polyesterlaminates, enabling the treated paperboard to be more readily formedinto containers without rupture thereof. In contrast to the use ofpaperboard/polyester laminates, the fluorochemical copolymer-treatedpaperboard does not tend to stick to the heated steel dies used inpress-forming tray manufacturing operations. Both sides of thefluorochemical copolymer-treated paperboard readily receive printingink. In contrast, it is difficult to perform printing operations uponthe polyester side of paperboard/polyester laminates. In addition, scrapfluorochemical copolymer-treated paperboard which is left over from thecontainer-forming operation can be repulped and reused, unlike scrapfrom container-forming operations employing paperboard/polyesterlaminates.

The treated paperboard containers can be filled with food and storedusing conventional techniques. Cooking of food in such containers isalso carried out in conventional fashion, but the elevated hightemperature oil and water repellency of the paperboard containers willenable use of high temperatures (e.g., 230° C.), long cooking times(e.g., two hours or more), and cooking of foods (e.g., spinach) whichhave been prone to cause oil or water staining in paperboard containersheretofore employed.

The above-described fluorochemical copolymers have also been found to beuseful for imparting soil resistance and oil and water repellency totextiles (e.g., polyester carpet fibers). The fibers (or yarn) can betreated as such or in an aggregated form (e.g., skein or roving) withthe fluorochemical copolymer, or the fabricated textile (e.g., articlessuch as carpet and woven fabrics) can be treated with the fluorochemicalcopolymer. The treatment can be carried out by applying thefluorochemical copolymer by known techniques customarily used inapplying fluorochemicals to fibrous substrates. For textile applicationdependent on substantial exhaustion of the fluorochemical copolymer fromthe treating medium, the concentration of copolymer in the exhaustionbath generally will be about 0.001 to 0.1 weight percent. Forapplications not involving exhaustion, e.g., padding, spraying, etc.,higher concentrations will be needed. The amount of fluorochemicalcopolymer deposited on the treated textile irrespective of theparticular mode of application will be, functionally speaking,sufficient to impart the desired degree of oil and water repellency, andgenerally this amount will be 0.02 to 3, preferably 0.06 to 0.16 weightpercent, or, expressed in terms of fluorine content, 0.01 to 1.5,preferably 0.03 to 0.08 weight percent fluorine.

The following examples are offered to aid understanding of the presentinvention and are not to be construed as limiting the scope thereof.

MONOMER EXAMPLE 1 Alcohol Preparation

In a 1 liter 3-neck flask equipped with a condenser, addition funnel,thermometer, mechanical stirrer, and electric heating mantle were placed276 g (6.0 moles) ethanol and 3.5 g SnCl₄. The resulting reactionmixture was heated with stirring to 55° C., the heating mantle wasremoved, and 462.5 g (5.0 moles) epichlorohydrin was added dropwise tothe flash over a 3 hour period while maintaining the reactiontemperature at about 55° to 60° C. After completion of the addition,stirring was continued for about 1 hour. Gas chromatographic analysis ofa portion of the reaction mixture indicated a yield of about 90 weight %of C₂ H₅ OCH₂ CH(CH₂ Cl)OH and about 9 weight % of C₂ H₅ O[CH₂ CH(CH₂Cl)O]₂ H. A solution of 5 g Na₂ CO₃ in 12 ml water was added to theflask. Excess ethyl alcohol and water were distilled from the reactionmixture. The reaction mixture remaining in the flask was filtered toyield about 660 g mixed chloromethyl alcohols. The pure monochloromethylalcohol C₂ H₅ OCH₂ CH(CH₂ Cl)OH was obtained by distillation (b.p.65°-70° C. at 2 torr).

Acrylate Preparation

In a 500 ml flask equipped as described above (but unheated) were placed69.2 g (0.5 mole) distilled C₂ H₅ OCH₂ CH(CH₂ Cl)OH, 100 g CH₂ Cl₂, 70.7g (0.7 mole) triethylamine, and 0.015 g monomethyl ether ofhydroquinone. To the resulting mixture was added dropwise, over a onehour period with stirring, a solution of 63.3 g (0.7 mole) acryloylchloride in 100 g CH₂ Cl₂. The temperature of the reaction mixture wasallowed to rise to about 35° C. during the acryloyl chloride addition.The reaction mixture was stirred for about 30 minutes at ambienttemperature, and 120 ml water was added to the flask followed byaddition of a solution of about 5 g NaHCO₃ in 25 ml water. The phaseswere separated and the organic phase was washed twice with 50 ml portionof dilute aqueous NaCl solution. The organic phase was dried overanhydrous MgSO₄, concentrated under aspirator vacuum, and the residualacrylate product distilled. The product had a boiling point of 48°-53°C. at 0.2 torr, and was identified by IR and NMR spectroscopy as C₂ H₅OCH₂ CH(CH₂ Cl)OCOCH═CH₂. Gas chromatographic analysis indicated apurity of 98.7%.

MONOMER EXAMPLES 2-11

Using the general procedure of Monomer Example 1, several additionalmonomers were prepared. For Monomer Example 9, an alcohol was preparedusing methanol in place of ethanol in the Alcohol Preparation step ofMonomer Example 1, the resulting chloromethyl alcohol was reacted with a20 percent molar excess of chloroacetic acid in heptane, water wasremoved from the reaction mixture by azeotropic distillation, and theresulting product was identified as having the general formula:

    R.sup.1 O[CH.sub.2 CH(CH.sub.2 X)O].sub.n C(O)CH.sub.2 Cl  V

where R¹ is methyl, X is chlorine and n is 1. The monomer of Formula Vwas next reacted with acrylic acid in the presence of triethylamine toform the desired monomer. For Monomer Example 10, the general procedureof Monomer Example 1 was followed but methacryloyl chloride wassubstituted for acryloyl chloride in the Acrylate Preparation step. InMonomer Example 11, the general procedure of Monomer Example 1 wasfollowed but a 4:3 molar ratio of epichlorohydrin to methanol was usedin the Alcohol Preparation step.

Set out below in Table A are the monomer produced and, where measured,boiling points for the monomers of Monomer Examples 2 through 11.

                                      TABLE A                                     __________________________________________________________________________    Monomer                       Boiling point,                                  Example                                                                             Monomer                 °C. (torr)                               __________________________________________________________________________    2     CH.sub.3 OCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2                                                  53-54 (0.5)                                     3     CH.sub.3 C.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2          2                       55-60 (0.2)                                     4     (CH.sub.3).sub.2 CHOCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2                                        60-64 (0.2)                                     5     CH.sub.3 C.sub.3 H.sub.6 OCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2          1                       71-75 (0.2)                                     6     (CH.sub.3).sub.3 COCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2                                         56-62 (0.2)                                     7     (CH.sub.3).sub.2 CHC.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCH.db          d.CH.sub.2              77-80 (0.2)                                     8     ClC.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCH═CH.sub.2                                         80-85 (0.2)                                     9     CH.sub.3 OCH.sub.2 CH(CH.sub.2 Cl)OC(O)CH.sub.2 OCOCH═CH.sub.2                                    98-107 (0.4)                                    10    CH.sub.3 OCH.sub.2 CH(CH.sub.2 Cl)OCOC(CH.sub.3)═CH.sub.2                                         52-55 (0.2)                                     11    CH.sub.3 O[CH.sub.2 CH.sub.2 CH(CH.sub.2 Cl)O].sub.1-3 COCH═CH.s          ub.2                    --                                              __________________________________________________________________________

Several monomers of the invention were used to prepare fluorochemicalcopolymers. The fluorochemical copolymers were applied to cellulosicmaterials or to textile fibers, and the oil and water repellency of theresulting substrates was evaluated, as shown in the Copolymer Examplesset forth below.

COPOLYMER EXAMPLE 1 Preparation of Copolymer Emulsion

The following ingredients were placed in a screw-capped, 115 ml glassbottle, in the amounts set forth below in Table I:

                  TABLE I                                                         ______________________________________                                        Ingredient              Amount, g                                             ______________________________________                                        C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.4 OCOCHCH.sub.2                                    21.0                                                  C.sub.2 H.sub.5 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                5.4                                                    ##STR6##               1.5                                                   CH.sub.2C(CH.sub.3)COOC.sub.2 H.sub.4 N.sup.+ (CH.sub.3).sub.3                Cl.sup.-(a)             1.2                                                   n-Octanethiol           0.06                                                  C.sub.18 H.sub.37 N.sup.+ (CH.sub.3)(C.sub.2 H.sub.4 O).sub.x H(C.sub.2       H.sub.4 O).sub.y H Cl.sup.-,                                                                          0.9                                                   x + y = 15.sup.(b)                                                            2,2'-Azobis(isobutyramidine) dihydrochloride.sup.(c)                                                  0.15                                                  Deionized water         52.5                                                  Acetone, reagent grade  17.5                                                  ______________________________________                                         .sup.(a) "Sipomer Q6-75", commercially available from Alcolac, Inc.           .sup.(b) "Ethoquad 18/25", commercially available from Armak Industrial       Chemical Division of Akzona, Inc.                                             .sup.(c) "V50", commercially available from Crescent Chemical Co.        

The glass bottle and its contents were briefly subjected to reducedpressure to remove oxygen. The glass bottle was then flushed withoxygen-free nitrogen, sealed, placed in a water bath maintained at 72°C., and tumbled for 16 hours. A 95 percent yield of fluorochemicalcopolymer was obtained as an aqueous emulsion containing about 29percent solids.

COPOLYMER EXAMPLE 2 Preparation of Fluorochemical Copolymer-treatedPaperboard

A 390 gram mixture of bleached sulfate wood pulp containing equal partsof "Alberta HiBrite" softwood pulp and "Marathon" hardwood pulp wasplaced in a 0.68 kg "Voith" laboratory beater apparatus with 23 litersof water. The resulting mixture was refined for 80 minutes to yield apulp having a Canadian Standard Freeness of 450 to 500, as measuredaccording to TAPPI Standard No. T227-05-58. The refined wood pulpsuspension was then diluted with an equal volume of water to form asuspension containing about 0.8 percent by weight solids. The dilutedsuspension was stirred with an electric mixer, and 1250 ml of thestirred mixture (containing about 10 g of refined fiber) was removed andplaced in a 2 liter graduated cylinder. A 0.15 g portion of cationicpolymeric retention aid ("Betz 1275", commercially available from BetzLaboratories Inc.) was mixed with the contents of the graduatedcylinder. Next, 0.12 g (0.04 g on a solids basis) of the fluorochemicalcopolymer of Copolymer Example 1 was added to the graduated cylinder,followed by mixing. The resulting fiber suspension was poured into a30.5 cm×30.5 cm paper handsheet mold having an 80 mesh stainless steelscreen (commercially available from Williams Apparatus Co.) andcontaining 10 liters of water. The perforated stirrer was moved up anddown 3 times to mix the fiber suspension and water, and the mold thendrained. The screen, wet handsheet and two paper blotters were pressedusing a hand roller. The screen was removed from the sheet, two paperblotters were placed on the wire side of the sheet, and the resultingassembly was squeezed in a hydraulic press at a pressure of 6.9 MPa. Thepressed handsheet was dryed in a 46 cm×51 cm sheet dryer (commerciallyavailable from Williams Apparatus Co.) that had been set at an initialtemperature of 150° C. After insertion of the pressed handsheet, thetemperature of the metal dryer plate decreased to about 100° C. Thehandsheet was removed after the plate temperature recovered to 120° C.and cut into thirds. One third was formed into a tray and evaluatedusing the procedure described below. Another third was aged by heatingin a forced air oven (commercially available from Despatch Oven Co.) at120° C. for 15 minutes, and the remaining third was aged byequilibrating at 22° C., 50% R.H. for 14 days. Each third of thehandsheet sample was cut into 12.7 cm×12.7 cm square sheets. The squaresheets were folded into square trays each having 2.5 cm deep sidewallsand a 7.7 cm×7.7 cm base.

The treated handsheet samples were evaluated for oil repellency byfilling two of each of the trays with corn oil ("Mazola", commerciallyavailable from Best Foods division of CPC International, Inc.) andplacing the filled trays (and enough other filled test trays to bringthe total number of filled test trays to 20) on a single oven rack in apreheated 204° C. electric oven for 30 minutes. Such temperatures andtimes exceed those generally used to evaluate existing fluorochemicaloligomer-treated paperboard. The heated trays were removed, emptied, andinspected on the outer surfaces of the sides, base, and corner creasesfor staining. The oil repellency of the treated handsheets was evaluatedvisually according to the following scale:

0=staining after trays filled and before tray heated

1=very heavy staining (of sides, bottom and creases)

2=heavy staining (mainly of bottom and creases)

3=moderate staining (mainly of creases)

4=staining of creases only

5=no staining.

The treated handsheet samples were evaluated for water repellency byfilling two each of the treated trays with 1 percent aqueous sodiumchloride solution and placing the trays (and enough other filled testtrays to bring the total number of filled test trays to 20) in a 204° C.electric oven for 30 minutes. The trays were removed and emptied, andevaluated for staining using the above criteria.

Set out below in Table II are the oil and water repellency ratingsobtained for each of the above-described handsheet samples.

                  TABLE II                                                        ______________________________________                                                            Repellency rating                                                               Corn      Aqueous                                       Handsheet sample      Oil       NaCl                                          ______________________________________                                        not aged              --        4                                             aged at 120° C. for 15 min.                                                                  4.5       5                                             aged at 22° C., 50% R.H. for 14 days                                                         4.5       4.5                                           ______________________________________                                    

The copolymer of Copolymer Example 1 was used to prepare additionalhandsheets with dimensions of 30.5 cm×30.5 cm×0.58 mm, containing about30 g refined treated fiber. The handsheets were unaged, and were formedinto trays as described above. Various commercial canned or frozen foodproducts containing oily or aqueous fluids were placed in the trays. Thefood-filled trays were heated in a conventional oven and the trays thenevaluated for staining using the above-described criteria. Set out belowin Table III are the food type, cooking conditions, and repellencyratings obtained.

                  TABLE III                                                       ______________________________________                                                  Cooking conditions.sup.2                                                                    Repellency                                            Food.sup.1  Temp.      Time     rating                                        ______________________________________                                        Spinach.sup.3                                                                             204° C.                                                                           30 min.  4                                             Spinach.sup.4                                                                             204° C.                                                                           30 min.  2                                             Green beans.sup.5                                                                         204° C.                                                                           30 min.  4.5                                           Green beans.sup.6                                                                         204° C.                                                                           30 min.  5                                             Beef gravy.sup.7                                                                          204° C.                                                                           30 min.  5                                             Lasagna.sup.8                                                                             190° C.                                                                           30 min.  4.8                                           Fried chicken.sup.8                                                                       190° C.                                                                           30 min.  5                                             Pudding.sup.8                                                                             190° C.                                                                           30 min.  5                                             ______________________________________                                         .sup.1 Frozen foods were thawed before being placed in trays.                 .sup.2 Cooked in a conventional oven ("Kenmore" model 911.9337910 electri     range, commercially available from Sears, Roebuck and Co.) at the             indicated temperature and time.                                               .sup.3 "Libby's"  canned spinach, commercially available from Libby McNei     & Libby, Inc.                                                                 .sup.4 "Bird's Eye" frozen chopped spinach, commercially available from       Bird's Eye Co.                                                                .sup.5 "Green Giant" canned sliced green beans, commercially available        from Pillsbury Co.                                                            .sup.6 "Green Giant" frozen cut green beans in butter sauce, commercially     available from Pillsbury Co.                                                  .sup.7 "FrancoAmerican" canned beef gravy, commercially available from        Campbell Soup Co.                                                             .sup.8 "Swanson", commercially available from Campbell Soup Co.          

This example shows that fluorochemical copolymers derived from monomersof this invention provide excellent oil and water repellency onpaperboard, under both laboratory and actual food cooking conditions.

COMPARATIVE EXAMPLE 1

Using the method of Copolymer Examples 1 and 2, but using the monomer C₂H₅ OCH₂ CH(CH₃)OCOCH═CH₂ in place of the monomer C₂ H₅ OCH₂ CH(CH₂Cl)OCOCH═CH₂, a fluorochemical copolymer was prepared, exhausted ontocellulose fiber, made into paperboard, and evaluated. The treatedpaperboard exhibited an initial water repellency of 1.5, a waterrepellency after aging of 4.5, and an oil repellency after aging of 4.5.

This comparative example shows that substitution of anon-halomethyl-containing monomer for the monomer of Formula I provideda fluorochemical copolymer with low initial water repellency.

COPOLYMER EXAMPLES 3 to 10

Using the methods of Copolymer Examples 1 and 2, several fluorochemicalcopolymers were prepared, exhausted onto cellulose fiber, made intopaperboard, and evaluated both without aging and with aging at 120° C.in a forced air oven for fifteen minutes. Set out below in Table IV arethe copolymer charging ingredients and amount in grams of eachingredient for each Copolymer Example. Set out below in Table V are thepercent loading of fluorochemical copolymer solids on fiber, amount andtype of retention aid, and oil and water repellency ratings forpaperboard treated with the fluorochemical copolymers of Table IV.

These Copolymer Examples show the use of various monomers of Formula Ito prepare fluorochemical copolymers.

                                      TABLE IV                                    __________________________________________________________________________    Copolymer                  Copolymer Example no. and amount in grams          charging ingredients       3  4  5  6  7  8  9  10                            __________________________________________________________________________    C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.4 OCOCHCH.sub.2                                       21 21 21 21 21 21 21 21                            CH.sub.3 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                          5.4                                                CH.sub.3 C.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                             5.4                                             (CH.sub.3).sub.2 CHOCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                      5.4                                          CH.sub.3 C.sub.3 H.sub.6 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                   5.4                                       (CH.sub.3).sub.3 COCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                             5.4                                    (CH.sub.3).sub.2 CHC.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                               5.4                                 ClC.sub.2 H.sub.4 OCH.sub.2 CH(CH.sub.2 Cl)OCOCHCH.sub.2                                                                   5.4                              CH.sub.3 OCH.sub.2 CH(CH.sub.2 Cl)OC(O)CH.sub.2 OCOCHCH.sub.2                                                                 5.4                            ##STR7##                  1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                           CH.sub.2C(CH.sub.3)COOC.sub.2 H.sub.4 N.sup.+ (CH.sub.3).sub.3 Cl.sup.-                                  1.2                                                                              1.2                                                                              1.2                                                                              1.2                                                                              1.2                                                                              1.2                                                                              1.2                                                                              1.2                           N.sub.2 [C(CH.sub.3).sub.2 C(NH.sub.2)NH.HCl] .sub.2                                                     0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                                                                             0.15                          C.sub.18 H.sub.37 N.sup.+ (CH.sub.3)(C.sub.2 H.sub.4 O).sub.x H(C.sub.2       H.sub.4 O).sub.y H Cl.sup.-, x + y = 15                                                                  0.9                                                                              0.9                                                                              0.9                                                                              0.9                                                                              0.9                                                                              0.9                                                                              0.9                                                                              0.9                           n-C.sub.8 H.sub.17 SH      0.06                                                                             0.06                                                                             0.06                                                                             0.06                                                                             0.06                                                                             0.06                                                                             0.06                                                                             0.06                          Water                      52.5                                                                             52.5                                                                             52.5                                                                             52.5                                                                             52.5                                                                             52.5                                                                             52.5                                                                             52.5                          Acetone                    17.5                                                                             17.5                                                                             17.5                                                                             17.5                                                                             17.5                                                                             17.5                                                                             17.5                                                                             17.5                          __________________________________________________________________________

                  TABLE V                                                         ______________________________________                                                      Copolymer Example No.                                                         3   4     5     6   7   8   9   10                              ______________________________________                                        % Copolymer on fiber                                                                          0.4   0.4   0.4 0.4 0.4 0.4 0.4 0.4                           Retention aid, % on fiber                                                     .sup.(a) Polymeric cationic                                                                   2.0   1.5   1.5 2.0 2.0 1.5 2.0 2.0                           aliphatic amide                                                               Repellency rating                                                             Corn oil after aging                                                                          4.8   4.3   4.1 4.3 1   3.5 5   4.8                           Aqueous NaCl before aging                                                                     4.5   4.5   4.3 4.5 4   4.8 4.3 3.5                           Aqueous NaCl after aging                                                                      5     4.8   4.9 5   4.5 5   5   5                             ______________________________________                                         .sup.(a) "Betz 1275", commercially available from Betz Laboratories, Inc.

COPOLYMER EXAMPLE 11

To evaluate the utility as a textile treatment of a fluorochemicalcopolymer derived from a monomer of this invention, a loosely knittedfabric of carrierless polyester staple carpet yarn (12 denier perfilament) was treated with a padding bath containing 0.74 wt. % of thefluorochemical copolymer of Copolymer Example 1, to provide 0.22% solidson fiber. The treated fabric was dried for 15 minutes at 160° C.,disperse dyed using a "Launder-Ometer" laboratory dyeing machine (ModelLEF, commercially available from the Atlas Electric Devices Company),and dried for 10 minutes at 130° C. The treated fabric was found to havean oil repellency rating of 3 as measured using AATCC Standard Test118-1978 (modified by waiting 10 seconds instead of 30 seconds beforemeasuring oil repellency). The aqueous stain repellency of the treatedfabric was measured using a water/isopropyl alcohol test. In such test,aqueous stain repellency is expressed in terms of the "WATER/IPA" ratingof the treated fabric. Treated fabrics which are penetrated by orresistant only to a 100% water/0% isopropyl alcohol mixture, the leastpenetrating of the test mixtures, are given a rating of 100/0, whereastreated fabrics resistant to a 0% water/100% isopropyl alcohol mixture,the most penetrating of the test mixtures, are given a rating of 0/100.Other intermediate values are determined by use of other water/isopropylalcohol mixtures, in which the percentage amounts of water and isopropylalcohol are each multiples of 10. The WATER/IPA rating corresponds tothe most penetrating mixture which does not penetrate or wet the fabricafter 10 seconds contact. In general, a WATER/IPA rating of <50/>50 isdesirable. The treated fabric of this example had a WATER/IPA rating of40/60.

The resistance of the treated fabric to loss of performance duringdyeing was evaluated by measuring the fluorine content of the treatedfabric before and after dyeing. The treated fabric had 756 ppm fluorinebefore dyeing and 743 ppm fluorine after dyeing, indicating that nearly100 percent of the fluorochemical copolymer was retained on the fabricafter dyeing.

Various modifications and alterations of this invention will be apparentto those skilled in the art without departing from the scope and spiritof this invention and the latter should not be restricted to that setforth herein for illustrative purposes.

What is claimed is:
 1. A compound having the formula:

    R.sup.1 O[CH.sub.2 CH(CH.sub.2 X)O].sub.n [C(O)CH.sub.2 O].sub.m COCR.sup.2 ═CH.sub.2

wherein R¹ is a halosubstituted C₁₋₂₀ alkyl or a halosubstituted orunsubstituted C₁₋₂₀ cycloalkyl or aralkyl group which can containdivalent catenary oxygen or sulfur atoms, R² is H or methyl, X is ahalogen atom, n is 1 to about 10, and m is zero or
 1. 2. A compoundaccording to claim 1, wherein R¹ is a C₁₋₂₀ cycloalkyl, haloalkyl, orhalocycloalkyl group and R² is H.
 3. A compound according to claim 1,wherein R¹ is a C₁₋₅ haloalkyl radical.
 4. A compound according to claim1, wherein R² is H.
 5. A compound according to claim 1, wherein X ischlorine.
 6. A compound according to claim 1, wherein n is 1 to about 3.7. A compound according to claim 1, wherein m is zero.
 8. A compoundhaving the formula:

    R.sup.1 O[CH.sub.2 CH(CH.sub.2 X)O].sub.n C(O)CH.sub.2 OCOCR.sup.2 ═CH.sub.2

wherein R¹ is a halosubstituted or unsubstituted C₁₋₂₀ alkyl,cycloalkyl, or aralkyl group which can contain divalent catenary oxygenor sulfur atoms, R² is H or methyl, X is a halogen atom, and n is 1 toabout
 10. 9. The compound R¹ O[CH₂ CH(CH₂ Cl)O[₁₋₃ C(O)CH₂ OCOCH═CH₂according to claim 8, wherein R¹ is CH₃ -- or CH₃ CH₂ --.
 10. A compoundhaving the formula:

    R.sup.1 O[CH.sub.2 CH(CH.sub.2 X)O].sub.n [C(O)CH.sub.2 O].sub.m COCR.sup.2 ═CH.sub.2

wherein R¹ is a halosubstituted or unsubstituted C₁₋₂₀ alkyl,cycloalkyl, or aralkyl group which can contain divalent catenary oxygenor sulfur atoms, R² is H or methyl, X is a halogen atom, n is 3 to about10, and m is zero or 1.